Insecticides



easel My invention insecticides l iereiii insecticide or larvacicle cu afy ibe scribed cei e lie ii in the L'1olecu"-, the resultant in coron seoticide is extremely tae'eous for use. signed to continue the formerly filed spplicati l, and to cite examples of certaie of the suitstances various broad class s defined ill my application.

In my experiments l[ have found that Where the fluorine is directly linked to nitrogen in the molecule, the fluorine is readily available for its insecticidal effect, and is therefore more desire-isle than other forms of compounds in which he fluorine forms part a coruoler. ion or rodicol such as in the case of the fluosilicates. l are aware that various compounds have previously been formed and used as insecticides, such as inorganic fluorides and various fluosilicates, The present invention, however, is limited to organic compounds in which the nitrogen is directly linked to the fluorine in the molecule.

Among the various compounds which I have found effective for mothproofing and insecticidal purposes are included the primary, secondary, and tertiary amines and polyamines of pure hy drocarhoris or hydrocarbons having suhstitueut atoms, groups, or radicals in. their structure. ll have already'described and claimed the fluorides of the alkylamihes and the hydrosyalliylamines in my previously filed application a cove Monti fled. As an example of such a substance, II cited a mixture of mono-, di-, and tri-ethar1olauunonlum fluoride.

As examples of substances embraced by sud (I I? l Muse,

Words, ammonium present ooullcotlou, l; the iollowing general "es, t early us "stood that it would i ractical to list compound which Woulu lie in these classes. As insecticities, i desire the hydrofiuuio acid addition compounds or" the allrylamines with or without substi'imerlt g oups, atoms, or adicals in their structure. It 1 Sher desire as secticides the hydrofluoric acid addition comoouuds of the ammonia rise to primary, ry amines and polyamines of i. use: eltieues, alkiues, homocyclie A o sud polycyclic), and polyhucleer aliphatic compounds, with omluo groups either in the aromatic or aliphatic ring, aromatic residues, heterocyclic residues in 5 forms a oi the nucleus, heterocyc dues "n which i trogen forms a part of the eucle is, heterocyclic compounds containing more i u one nitrogen in their nuclei, and

ollralolds.

The present irrventiouthus embodies the hydrofluorides or organic hases in which the fluorine directly linked to nitrogen or in other fluoride substituted compounds in which one or more of the hydrogens attached the nuclear nitrogen. are substituted by the above mentioned residues. The products may also be defined as hydrofluoric acid addi--- tiori compounds of the amines and polyamines,

oi the residues mentioned above.

In order that the various compounds which ere capable of acting as insecticides may be clearly understood, it am providing the follovvim: groups of eireroples of specific compounds givine the formula, the name, the volume and page on which these compounds ere listed in Beilsteins .Z-laudlouch de Oreanischeu Chemie. I desire use the hydrofluorides of the following compounds or any of their derivatives. These examples are only representative of the type of compounds which I desire to protect, and comprise by lllU means a complete description of all of the compounds I intend to use.

its an example of alirylamlnes having substituent groups, atoms, or radicals in their structure, the suhstitueuts being other than hydroxyl, I list l'ollotrlue:

n I Formula Name Volume Page H: Cl H: 2chloro-l,3- IV 2-33 CC-C diumino pro- H pane. NH: N H:

GHr-CHgNHCH: 2bromo-l-methyl- IV 134 amino ethane.

CH! 3 bromo-2 umlno IV 178 oentano. CHsCHICHBi' ENE:

H: N09 Hg 2 nltro-l.3-bls(dl- IV 263 C C-C methyl-amino) I m linemen hum), p pm i As examples of alkenamines, I propose the fol lowing: I also desire to protect their isomers, the amino, imino, or substituted amino groups cepable of forming addition compounds with bydrofluoric acid.

As an example of unsetureted cyclic oompoumls, I propose the following:

Formula Name l Volume Page CH:=CHCH;NH1 Allylamine IV 205 CH=CHCH1CH1NH; Allflomcthylumlne. IV 220 CB;CH=CHCH;NH1 Crotylemiue IV 22! CHFCHCH1CH(CH2CHCH:)|-CH:NH3 l amino-4 methyl hepiudlono (1, 6 IV 221) As examples of alkines capable of forming a fluorine to nitrogen linkage, I propose the following:

Formula Name Volume Pece CHEGHNH, Aoetyleneamine IV 2238 CHECHCHzNH: Propargylaminew. IV 228 As an example of polycyclic (cllcyclic) min- 39 pounds, I propose the following:

Formula Name Volume Page -eminoa methyl blcycllc x11 31 1,2,3 octeuo.

As examples of diemines and polyemines, I list the following:

amino propane.

As an example of complex substituted amines or tertiary amines I propose the following:

As examples of aromatic amines, I- propose the (i l following:

Formula I Name Volume Page Aniline XII 59 H Orthm, meta and para- XII 1147 C Hzr-C-C H! isopropyl aniline.

J As examples of unsaturated side chain arometic amines, I propose the following:

CH2=C(CH3)CH2CH(OH)CH2CH(CH3)N(CI'I3)2 Fm'mula Name Volume Page 6-dimethy1amines-2-6 dimethyl heptene 1-01 (4) NH 2m 1 ml Volume IV, page 301. I CH a As an example of mono and polycyclic corn 5 pounds, I propose the following:

NH; Zemlno stllbene.-. K11 1132 65 B H Formula Name Volume Page C=C NH, 2acetylene aniline. K11 1210 CH: Cyclopropylamine..... XII 3 CECE l CHNH: 70

CH CH cclb 'll x y 0 m m u 4 As examples of aromatic amines and their dom rivetives formed by the substitution of some of the hydrogens in the residues by other negative mmrm m" ggxrmlm mi amm 3t :fmmw mm mumps either in the aromatic nu- 01 my aliphatic ring 1, I propose the follow- 6 7 a m m m 1 w m m 2 a a m w ,7, M H H 1 S, H 1 E m P e m nu B e I m n u m m n u v v v w w v N m x x a 10 X m m X x X x x x V V D. V o m w w... l U n u n n n 0 a n W v. m "w u u n n n n h u n n n m u E U u u u 0 u a c m e m u n h a m m m m z mm a N m m m u u u m w Aw u n u n a w o h m N .m E 6 h M m a w w w mm n U n m n m, h .m m n E rw n a h m n .m P u mm 5 we 3 n m m u y H M 2 Z w n m m L a h .m m w m m u v. m w. m m (1m n W n m w a y a a w W 2 n o u m w L w a I b S M 1 m n P m w\ m m w w w n x w m m m 1 m w 5 W i m r W 1.. h m m m m m y x .5 r T x w m w 4 NE W! A: P 1 B PW. m mu mu w T, m H H m a 2 2 WW 6 {u G 0 C H m w x E m vfillinn b "W I V m N N N m h mu HE R P n m m a N w 7 M u C N m r 1 355M, A n m M nu I b Ni!!! m m Wm a. v m Q ax l, hmvlrwwkw 1 v i 154 V54 N m H (E (w R w. t N m w E M m 0 m w MW m m & Wy 0 N .1 U W. Q N w m m m m v W J O, A; H t kWEJN F M m w W "m mzygen forms mm of the nucleus, I time mlmwmg mom's-1,

e rz sesz em Formuie Name Volume Page 2,2 dihydro phthnlmlne XXIII 136 -CH\\ C-NII H:

/ 3A bcnzopyridsxino 0:. clnzoiine v. XXIII 173 A AA I5 hmh-pyficlssbie phthclezinc XXIII we Bcnzo pyrimidine or quinomllne 1C; 175

N Beuzc pyrrzin XXIII 178 Pyridine pyridine ornapht'uyl'idin XXIII I77 H 2 methyl phennzine XXIII 237 N CH.

\ I II 2 methyldj pbenenthroiino XXIII 238 -I I 5 CF,

H Dlindolc. XXIII 253 As examples of alkaloids propose the following:

Name Volume Page Nicotine. XXIII 110 Quinineu'. XXIII 511 Cuticinc... XX VI It will be noted that all of the foregoing compounds have in common the fact that when combined with hydrofluoric acid they form a fluoride in which the fluorine is directly linked with nitrogen in the molecule. I have found that organic amines and the like when combined with hydrofiuoric acid will form compounds in which the fluorine is directly linked to nitrogen and have found that these substances in general act as insecticides.

In accordance with the patent statutes, I have described the insecticide I have discovered and the materials forming the same; and while I have endeavored to set forth the best embodiments thereof, I desire to have it understood that these are only illustrative of compounds which carry out my invention, and that obvious changes may he made within the scope of the following claims without departing from the spirit of my invention.

I claim:

1. An insecticide containing as an essential ingredient a fluoride of the amines and polyamines of alkyls having substituent atoms in their structure in which the fluorine atom is directly linked to an amino nitrogen atom.

A moth-proofing substance including the fluorides of alkyl substituted ammonia in which the fluorine is directly linked with a nitrogen atom.

A moth-proofing substance including the fluorides of hydroxyalkyl substituted ammonias.

4. A moth-proofing substance comprisin a mixture of mono-. di-. and tri-cthanolammonium fluoride.

JOSE B. CALVA. 

